CN108329491A - A kind of stable thermosensitive polymer hydrogel - Google Patents
A kind of stable thermosensitive polymer hydrogel Download PDFInfo
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- CN108329491A CN108329491A CN201711479163.2A CN201711479163A CN108329491A CN 108329491 A CN108329491 A CN 108329491A CN 201711479163 A CN201711479163 A CN 201711479163A CN 108329491 A CN108329491 A CN 108329491A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/10—Silicon-containing compounds
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Abstract
The present invention provides a kind of stable thermosensitive polymer hydrogel, which is characterized in that includes the component of following parts by weight:8 22 parts of hydroxyethyl celluloses, 12 19 parts of N N-isopropylacrylamides, 15 parts of non-ionic celluloses ethers, 4 11 parts of xanthans, 37 parts of sodium chloride, 29 parts of phosphoric acid polyhexamethylene guanides, 0.8 2.5 parts of reinforcing fibers, 39 Schisandra chinensis kernel antibacterial peptides, 68 88 parts of pure water.The present invention has good bio-compatible type, mechanical property and mechanical strength, it more importantly can be high to thermotonus responsiveness in 37 50 DEG C of section, biological slow-released material, fast cooling material etc. are can be applied to, demand of the fields such as information, life, environment, aerospace for functional material is can adapt to.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of stable thermosensitive polymer hydrogel.
Background technology
Hydrogel can be defined as being swollen and keep large quantity of moisture in water and undissolved polymer, hydrophilic small molecules energy
It is enough to be spread in hydrogel.Hydrogel has good biocompatibility, compared with hydrophobic polymer, the enzyme that is immobilized or thin
Born of the same parents only have weaker interaction, and being fixed on the activity of biomolecule in hydrogel can be maintained for a long time.Therefore, hydrogel
In fields such as biochemistry, medicine, there are many purposes.
According to hydrogel to the response situation of environmental stimuli, hydrogel can be divided into two major classes:(1) " traditional " hydrogel,
This kind of hydrogel is insensitive to the variation of variation such as temperature and the pH of environment;(2) " environment sensitive " hydrogel, this kind of hydrogel
Stimulation caused by variation in quite wide degree to temperature or pH etc. has different degrees of response." traditional " water
Gel is the hot topic studied before people's the mid-80, and " environment sensitive " hydrogel has been then people since 1985 most
For interested project.
In addition, people are also especially interested in the hydrogel having the following properties that:(1) it environment can be decomposed in vivo
Hydrogel, such as the hydrogel that can be ablated under weak basic condition in vivo, the hydrogel that can be enzymatically decomposed;(2) can with from
The hydrogel of sub- exchanging form release protein;(3) hydrogel etc. with " memory ".Although the hydrogel type of people's research
It is various, but final purpose is desirable to hydrogel and plays a role in practical applications by different purposes and requirement.
In recent years, with the rapid development of the fields such as information, life, environment, aerospace science and technology, people are to material
The requirement of performance is higher and higher.Therefore, the functional polymer hydrogel material for being badly in need of having a collection of performance special comes out, existing to adapt to
For the trend of scientific technological advance.
Invention content
In view of this, the present invention provides a kind of stable thermosensitive polymer hydrogel, the present invention has good biofacies
Appearance type, mechanical property and mechanical strength, it is often more important that can be high to thermotonus responsiveness in 37-50 DEG C of section, it can
Applied to biological slow-released material, fast cooling material etc., the fields such as information, life, environment, aerospace are can adapt to for work(
The demand of energy material.
The technical scheme is that:A kind of stable thermosensitive polymer hydrogel, which is characterized in that including following weight
The component of number:8-22 parts of hydroxyethyl celluloses, 12-19 parts of n-isopropyl acrylamide, 1-5 parts of non-ionic celluloses ethers,
4-11 parts of xanthans, 3-7 parts of sodium chloride, 2-9 parts of phosphoric acid polyhexamethylene guanides, 0.8-2.5 parts of reinforcing fibers, 3-9 Schisandra fruits
Benevolence antibacterial peptide, 68-88 part pure water.
Further, the stable thermosensitive polymer hydrogel includes the component of following parts by weight:11-16 parts of hydroxyl second
Base cellulose, 14-17 part n-isopropyl acrylamide, 2-4 parts of non-ionic celluloses ethers, 6-9 parts of xanthans, 4-6 parts of chlorinations
Sodium, 4-7 parts of phosphoric acid polyhexamethylene guanides, 1.2-2.1 parts of reinforcing fibers, 5-8 Schisandra chinensis kernels antibacterial peptide, 75-85 parts of pure water.
Further, the stable thermosensitive polymer hydrogel includes the component of following parts by weight:14 parts of ethoxys
Cellulose, 15 parts of n-isopropyl acrylamide, 3 parts of non-ionic celluloses ethers, 8 parts of xanthans, 5 parts of sodium chloride, 6 parts of phosphoric acid are poly-
Hexa-methylene guanidine, 1.5 parts of reinforcing fibers, 7 Schisandra chinensis kernel antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 200-500um of the reinforcing fiber.
Particularly, the present invention can be prepared by this field any prior art.
The components such as heretofore described hydroxyethyl cellulose, n-isopropyl acrylamide can pass through prior art reality
It is existing.Non-ionic celluloses ether can be any one or mixing in hypromellose ether, hydroxypropylcelluloether ether.
Xanthans is also known as yellow glue, xanthan gum, and Xanthan Gum is that a kind of monospore generated by the fermentation of false xanthomonas is more
Sugar, through aerobic fermentation biotechnology, is cut by cabbage black rot xanthomonas campestris using carbohydrate as primary raw material
Disconnected 1,6- glycosidic bonds, after opening branch, in a kind of extracellular heteroglycan of acidity for being bonded to straight chain composition by Isosorbide-5-Nitrae-.Nineteen fifty-two by
The isolated Xanthomonas campestris pv. campestris of the United States Department of Agriculture Illinois Lilles Pi Ao the north research institute, and wild cabbage is made to carry
Object is taken to be converted into the water-soluble extracellular heteroglycan of acidity and obtain.Xanthans is to send out liquor-saturated through Xanthomonas campestris by carbohydrate, generation
The extracellular more pools of microorganism.Due to its macromolecular special construction and colloid property, and have multiple functions, can be used as emulsifier,
Stabilizer, gelling thickener, size, film forming agent etc., are widely used in all fields of national economy.
Phosphoric acid polyhexamethylene guanide has broad-spectrum;Effective concentration is low;Work fast;Property is stablized;It is soluble easily in water
Excellent performance;It can use at normal temperatures;It is long-term antibacterial, without side-effects;It is non-corrosive;It is colourless, odorless;It is nontoxic;It is non-ignitable, no
It is quick-fried, safe to use;It is moderate;Convenient transportation, it may be said that be best fungicide.
In the present invention, xanthans and sodium chloride synergistic can promote hydroxyethyl cellulose, n-isopropyl acrylamide and non-
The polymerizations of ionic cellulose ethers, crosslinking, be allowed to pure water in conjunction with and form hydrogel.Phosphoric acid polyhexamethylene guanide, increasing simultaneously
In the presence of strong fiber, stability when synergistic effect can improve moisture low temperature in macromolecule hydrogel system, and at 50 DEG C
The a large amount of release water outlets in left and right, to realize fast cooling;In addition phosphoric acid polyhexamethylene guanide can synergistic with Schisandra chinensis kernel antibacterial peptide
Effect significantly improves the anti-microbial property of the present invention, the sense of the microorganisms such as bacterium is can effectively avoid when applied to biomedicine field
Dye.
The macromolecule hydrogel structure of the present invention passes through ethoxy fibre using xanthans and sodium chloride synergistic as crosslinking agent
Dimension element, n-isopropyl acrylamide and non-ionic celluloses ether crosslinking are blended, and the height with temperature response characteristics is prepared
Molecule hydrogel.Meanwhile being blended in crosslinking and being added to reinforcing fiber, mechanical property and the machinery that can significantly improve the present invention are strong
Degree;The polyhexamethylene guanide of addition, as natural antimicrobial substance, can significantly improve the present invention's with Schisandra chinensis kernel antibacterial peptide
Anti-microbial property.
Inside of the invention has the three-dimensional net structure formed with chemical bond and/or physical force between macromolecular chain,
It is with good stability.Present invention can apply to the controlled release carrier of chemical sensor, drug or function ingredients, substances to detach,
The fields such as rapid cooling.
The mechanism that the present invention absorbs water is:The synergistic effects such as capillary attraction and dilating effect, chemistry and physisorption
As a result, wherein physical absorption accounts for leading role, the permeable pressure head inside and outside hydrogel cross-linked network is the key that its water swelling
Factor.
In the present invention, hydrone can form hydrogen bond with the functional group of core component, and high-sequential is formed in polymer surrounding
Water molecule layer, polymer is in extended configuration, when temperature is increased to 37-50 DEG C of temperature range(Lowest critical solution temperature
LCST)When, hydrogen bond is destroyed, and the hydrone being wrapped in around polymer is reduced, the heat resistance and salt tolerance between hydrophobic grouping
Enhancing, water are discharged from hole, gel sudden contraction, and deswelling occurs.The above change procedure is reversible, and the gel of contraction can be with
The reduction of temperature and be swollen again, restore to the original state.To realize that the rapid evaporation of moisture takes away heat, achieve the effect that cooling;
Or reach the drug component of internal carrying or function ingredients are released when the temperature rises, the effect etc. of long-acting slow-release.
The present invention has good bio-compatible type, mechanical property and mechanical strength, it is often more important that can be at 37-50 DEG C
Section it is high to thermotonus responsiveness, can be applied to biological slow-released material, fast cooling material etc., can adapt to information,
Demand of the fields such as life, environment, aerospace for functional material.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
It is only a part of the embodiment of the present invention to apply example, instead of all the embodiments.
Embodiment 1
A kind of stable thermosensitive polymer hydrogel, which is characterized in that include the component of following parts by weight:8 parts of ethoxy fibres
Tie up element, 12 parts of n-isopropyl acrylamide, 1 part of non-ionic celluloses ether, 4 parts of xanthans, 3 parts of sodium chloride, 2 parts of phosphoric acid poly- six
Methylene guanidine, 0.8 part of reinforcing fiber, 3 Schisandra chinensis kernel antibacterial peptides, 68 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 200um of the reinforcing fiber.
Embodiment 2
A kind of stable thermosensitive polymer hydrogel, which is characterized in that include the component of following parts by weight:22 parts of ethoxys
Cellulose, 19 parts of n-isopropyl acrylamide, 5 parts of non-ionic celluloses ethers, 11 parts of xanthans, 7 parts of sodium chloride, 9 parts of phosphoric acid
Polyhexamethylene guanide, 2.5 parts of reinforcing fibers, 9 Schisandra chinensis kernel antibacterial peptides, 88 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 500um of the reinforcing fiber.
Embodiment 3
A kind of stable thermosensitive polymer hydrogel includes the component of following parts by weight:11 parts of hydroxyethyl celluloses, 14 parts of N-
N-isopropylacrylamide, 2 parts of non-ionic celluloses ethers, 6 parts of xanthans, 4 parts of sodium chloride, 4 parts of phosphoric acid polyhexamethylene guanides,
1.2 parts of reinforcing fibers, 5 Schisandra chinensis kernel antibacterial peptides, 75 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 250um of the reinforcing fiber.
Embodiment 4
A kind of stable thermosensitive polymer hydrogel includes the component of following parts by weight:16 parts of hydroxyethyl celluloses, 17 parts of N-
N-isopropylacrylamide, 4 parts of non-ionic celluloses ethers, 9 parts of xanthans, 6 parts of sodium chloride, 7 parts of phosphoric acid polyhexamethylene guanides,
2.1 parts of reinforcing fibers, 8 Schisandra chinensis kernel antibacterial peptides, 85 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 400um of the reinforcing fiber.
Embodiment 5
A kind of stable thermosensitive polymer hydrogel includes the component of following parts by weight:14 parts of hydroxyethyl celluloses, 15 parts of N-
N-isopropylacrylamide, 3 parts of non-ionic celluloses ethers, 8 parts of xanthans, 5 parts of sodium chloride, 6 parts of phosphoric acid polyhexamethylene guanides,
1.5 parts of reinforcing fibers, 7 Schisandra chinensis kernel antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 300um of the reinforcing fiber.
Comparative example 1
A kind of stable thermosensitive polymer hydrogel includes the component of following parts by weight:14 parts of hydroxyethyl celluloses, 15 parts of N-
N-isopropylacrylamide, 3 parts of non-ionic celluloses ethers, 8 parts of xanthans, 5 parts of sodium chloride, 6 parts of phosphoric acid polyhexamethylene guanides,
1.5 parts of reinforcing fibers, 7 Schisandra chinensis kernel antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 300um of the reinforcing fiber.
Comparative example 2
A kind of stable thermosensitive polymer hydrogel includes the component of following parts by weight:14 parts of hydroxyethyl celluloses, 15 parts of N-
N-isopropylacrylamide, 3 parts of non-ionic celluloses ethers, 8 parts of xanthans, 5 parts of sodium chloride, 6 parts of phosphoric acid polyhexamethylene guanides,
1.5 parts of reinforcing fibers, 7 Schisandra chinensis kernel antibacterial peptides, 80 parts of pure water.
Further, the reinforcing fiber is basalt fibre.
Further, a diameter of 350um of the reinforcing fiber.
Macromolecule hydrogel performance test
The macromolecule hydrogel for choosing embodiment 1-5 and comparative example 1-2, the cm of 20 cm × 10 are prepared by the prior art
Shape(Water content is 100g).Macromolecule hydrogel is heated with 30 DEG C, 40 DEG C, 50 DEG C of temperature respectively, records its 12 points
Mass change in clock.Its result is as shown in table 1-3.
1. macromolecule hydrogel mass change value of table(30℃)
Experimental group/mass change(g) | 3min | 6 min | 9 min | 12 min |
Embodiment 1 | -0.8 | -1.5 | -1.9 | -2.0 |
Embodiment 2 | -0.6 | -1.4 | -1.7 | -1.7 |
Embodiment 3 | -1.5 | -1.9 | -2.0 | -2.1 |
Embodiment 4 | -1.0 | -1.8 | -1.9 | -2.0 |
Embodiment 5 | -0.3 | -0.7 | -1.4 | -2.4 |
Comparative example 1 | -2.8 | -4.5 | -9.0 | -18.5 |
Comparative example 2 | -3.0 | -5.1 | -11.1 | -16.3 |
2. macromolecule hydrogel mass change value of table(40℃)
Experimental group/mass change(g) | 3min | 6 min | 9 min | 12 min |
Embodiment 1 | -0.6 | -1.5 | -1.8 | -1.9 |
Embodiment 2 | -0.7 | -1.5 | -1.7 | -1.9 |
Embodiment 3 | -1.5 | -2.0 | -2.4 | -3.1 |
Embodiment 4 | -1.7 | -1.9 | -2.1 | -2.9 |
Embodiment 5 | -1.0 | -2.0 | -2.6 | -3.5 |
Comparative example 1 | -3.0 | -5.1 | -10.6 | -20.5 |
Comparative example 2 | -3.1 | -5.6 | -16.4 | -24.3 |
3. macromolecule hydrogel mass change value of table(50℃)
Experimental group/mass change(g) | 3min | 6 min | 9 min | 12 min |
Embodiment 1 | -12.9 | -17.4 | -24.6 | -31.3 |
Embodiment 2 | -12.2 | -15.3 | -22.4 | -29.3 |
Embodiment 3 | -10.4 | -16.4 | -21.5 | -28.7 |
Embodiment 4 | -10.0 | -16.1 | -22.4 | -28.4 |
Embodiment 5 | -12.0 | -18.1 | -26.4 | -30.0 |
Comparative example 1 | -3.9 | -8.0 | -15.3 | -20.9 |
Comparative example 2 | -6.2 | -11.7 | -17.2 | -25.4 |
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, and do not carrying on the back
In the case of spirit or essential attributes from the present invention, the present invention can be realized in other specific forms.Therefore, no matter from which
From the point of view of a bit, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is wanted by appended right
Ask rather than above description limit, it is intended that by all changes that come within the meaning and range of equivalency of the claims
It is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.It is noted that the technical characteristic not being described in detail in the present invention, can pass through this
Field any prior art is realized.
Claims (5)
1. a kind of stable thermosensitive polymer hydrogel, which is characterized in that include the component of following parts by weight:8-22 parts of hydroxyls
Ethyl cellulose, 12-19 part n-isopropyl acrylamide, 1-5 parts of non-ionic celluloses ethers, 4-11 parts of xanthans, 3-7 parts of chlorine
Change sodium, 2-9 parts of phosphoric acid polyhexamethylene guanides, 0.8-2.5 parts of reinforcing fibers, 3-9 Schisandra chinensis kernels antibacterial peptide, 68-88 parts of pure water.
2. stable thermosensitive polymer hydrogel according to claim 1, which is characterized in that including following parts by weight
Component:11-16 parts of hydroxyethyl celluloses, 14-17 parts of n-isopropyl acrylamide, 2-4 parts of non-ionic celluloses ethers, 6-9 parts
Xanthans, 4-6 part sodium chloride, 4-7 parts of phosphoric acid polyhexamethylene guanides, 1.2-2.1 parts of reinforcing fibers, 5-8 Schisandra chinensis kernel antibacterials
Peptide, 75-85 part pure water.
3. stable thermosensitive polymer hydrogel according to claim 2, which is characterized in that including following parts by weight
Component:14 parts of hydroxyethyl celluloses, 15 parts of n-isopropyl acrylamide, 3 parts of non-ionic celluloses ethers, 8 parts of xanthans, 5 parts
Sodium chloride, 6 parts of phosphoric acid polyhexamethylene guanides, 1.5 parts of reinforcing fibers, 7 Schisandra chinensis kernel antibacterial peptides, 80 parts of pure water.
4. stablizing thermosensitive polymer hydrogel according to claim 1-3 any one of them, which is characterized in that the enhancing is fine
Dimension is basalt fibre.
5. stable thermosensitive polymer hydrogel according to claim 4, which is characterized in that the diameter of the reinforcing fiber
For 200-500um.
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Cited By (2)
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CN109971487A (en) * | 2019-03-12 | 2019-07-05 | 山西大学 | A kind of soil-repairing agent and preparation method thereof with absorbent function |
CN116041797A (en) * | 2022-12-21 | 2023-05-02 | 山东科技大学 | Temperature-sensitive composite gel for preventing spontaneous combustion of mine coal and preparation method thereof |
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CN102634047A (en) * | 2012-05-16 | 2012-08-15 | 苏州宜生生物技术有限公司 | Preparation method of macromolecule hydro-gel |
CN102827441A (en) * | 2012-06-30 | 2012-12-19 | 安徽安生生物化工科技有限责任公司 | Cooling gel sheet |
CN105664250A (en) * | 2016-01-27 | 2016-06-15 | 苏州佰通生物科技有限公司 | Injectable and degradable thermo-sensitive hydrogel and preparation method thereof |
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CN101186673A (en) * | 2007-11-16 | 2008-05-28 | 天津工业大学 | Method for producing ultraviolet radiation-temperature response type macromolecule hydrogel |
CN102634047A (en) * | 2012-05-16 | 2012-08-15 | 苏州宜生生物技术有限公司 | Preparation method of macromolecule hydro-gel |
CN102827441A (en) * | 2012-06-30 | 2012-12-19 | 安徽安生生物化工科技有限责任公司 | Cooling gel sheet |
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CN109971487A (en) * | 2019-03-12 | 2019-07-05 | 山西大学 | A kind of soil-repairing agent and preparation method thereof with absorbent function |
CN116041797A (en) * | 2022-12-21 | 2023-05-02 | 山东科技大学 | Temperature-sensitive composite gel for preventing spontaneous combustion of mine coal and preparation method thereof |
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